Mordanting of acid dyes



polymeric mordants also present diflicu'lties.

United States Patent 3,271,148 MORDANTING OF ACID DYES Keith E.Whitmore, Rochester, N.Y., assignor to Eastman Kodak Company, Rochester,N.Y., a corporation of New Jersey No Drawing. Filed July 19, 1962, Ser.No. 211,095 22 Claims. (Cl. 96-29) This invention relates to dyemordanting layers and more particularly, to dye mordanting layers usefuleither integral with or contiguous to photographic color elements.

Mordanting, and thus immobilizing, soluble dyes in hydrophilic polymericcolloids such as gelatin, which are commonly employed as thefilm-forming colloids in phodye-mordanting polymers usually contain somelow molecular weight material which can cause trouble by diffusinglaterally within the layer or by migrating into an adjacent layer. Thisis particularly serious when the dye is being deposited as a pattern orimage.

Nonpolymeric mordant compounds offer some obvious advantages. Compoundsof this type, having a uniform composition, are easier to prepare andpurify than polymeric mordants, and changes in structure and inconcentration can be made without modifying the chemistry of thepolymeric ingredients of the layer. However, non- Not only are thephysical, chemical, and photographic properties of the colloidfrequently affected adversely by the saltforming groups, but hydrophobicballast groups of such mordant compounds to reduce its diffusibility inthe hydrophilic colloid vehicle decrease compatibility with the colloidso that it is difficult to prepare a stable, homogeneous dispersion.Furthermore, the combination of a hydrophobic ballast group and asalt-forming group often imparts surfactant and emulsifying propertiesto the mordant so that excess mordant may emulsify the contiguousmordanted dye and cause it to deteriorate and to wander.

It is an object of this invention to provide novel dyemordanting layersin which are utilized the advantages, but which overcome theshortcomings, of nonpolymeric ionic mordants.

It is another object of our invention to provide a new hydrophilicfilm-forming colloid containing at least one cationic, organic,nonpolymeric stabilized and immobilized mordant for acid dyes.

It is another object of the invention to provide new photographic dyemordanting compositions.

It is another object of the invention to provide a new photographicelement having at least one dye-mordanting layer comprising ahydrophilic polymer containing a nonpolymeric cationic mordant.

It is another object of the invention to provide a novel receivingelement for acid dyes.

It is another object of the invention to prepare by a novel processmordanted dye images of improved color characteristics and stability tolight and heat.

It is still another object of this invention to provide a novelphotographic color diffusion transfer process.

These and other objects of the invention are accom plished withmordanting compositions comprising at least "ice one hydrophilic organiccolloid containing a finely-divided, uniform dispersion of droplets orglobules of a highboiling, water-immiscible, organic solvent in which isdissolved a high concentration of a cationic, nonpolymeric, organicdye-mordanting compound for acid dyes.

Such mordanting compositions have particular utility in the photographicart and can be directly coated on a photographic support to serve as adye receiving sheet, or as an overlayer or interlayer on photographicelements, or added to photographic emulsion layers. The mordantingcompositions of the invention are especially useful for preparingelements for receiving and mordant ing diffusible acid dye images inphotographic color diffusion transfer processes.

Incorporating the nonpolymeric organic cationic mordants in layersaccording to our invention results in (1) reducing diifusibility of themordanting compound and of the mordanted dye, (2) increasing thestability to light and heat of the mordanted dye, (3) insulating themordant to render it physically, chemically, and photographically inertto materials outside the droplets, and (4) improvement in the density ofthe mordanted dye images.

The mordant utilized in practicing the invention can be widely varied.The choice of the mordant is generally dictated by practicalconsiderations familiar to those skilled in the art, e.g., expediency inpreparation of the compound, solubility in organic solvent, types ofdyes used, absorption of the dye-mordant salt, types of hydrophiliccolloid used, light fastness of the dyes used, and the like.

The nonpolymeric organic mordant compounds useful in our invention havecationic groups which are capable of entering into salt-formingreactions, e.g., a quaternary ammonium group and at least onehydrophobic group, which inhibits wandering, e.g., a long chainaliphatic group. Such cationic mordant compounds are well-known to thoseskilled in the art andcan be either water soluble or water insoluble.

Basic or cationic mordant compounds useful in the dyemordantingcompositions of our invention for immobilizing soluble acid dyes,include quaternary ammonium and phosphonium, and ternary sulfoniumcompounds in which there is linked to the N, P, or S, onium atom atleast one hydrophobic ballast group, such as long chain alkyl orsubstituted alkyl groups. The onium atom can be part of an open chain orof a heterocyclic ring and there can be more than one onium atom in themolecule.

Typical cationic mordants which are useful in our invention include thefollowing compounds which are referred to hereinafter by number asindicated:

TABLE I.CATIONIC MORDANT COMPOUNDS (1) Octadecyltri-n-butylammoniumbromide.

(2) Tetradecyltri-n-butylammonium bromide.

(13) Octadecyltri-n-octylammonium bromide.

(4) Octadecyltri-n-decylammonium bromide.

(5 Methyltri-n-laurylammonium p-toluenesulfonate.

(6) Methyltri-n-decylammonium p-toluenesulfonate.

(7) Tetra-n-octylamm-onium bromide.

(8) Tetra-n-decylammonium bromide.

(9) Tetra-n-laurylammonium bromide.

-( 10) N,N-dimethyl-N- (B-hydroxyethyl) -N- ("y-stealarnidopropyl)ammonium dihydrogen phosphate.

( 1 1 N,N-dirnethyl-N-(B-hydroxyethyl -N- ('y-stearoyloxypropyl)ammonium chloride.

( 12) N,N-dimethyl-N-(B-hydroxyethyl -N-(p-tertoctylphenoxydiethoxyethyl) -ammonium methosulfonate.

( 13 N,N-dimethyl-N- ,B-hydroxyethyl -N-(p-tertoctylphenoxytetraethoxyethyl)-ammonium methosulfonate.

3 TABLE I.Continued l4) N,N-dimethyl-N-( 8-hydroxyethyl)-N-(N-methyl-'y-stearamidopropyl) ammonium bromide.

() Cetyltrimethylammonium bromide.

(16) 17,17,20,20,31,31,34,34-octamethyl-17,20,31,34-

tetrazapentacontaniumtetrabromide.

(17) 1,4-dihexadecyl-1,4,-diazabicyclo [2.2.2] octanium dichloride.

(18) 1,4-didodecyl-1,4-diazabicyclo[2.2.2]octanium p-toluene sulfonate.

(19) 1,4-bis['y-(2,4-di-tert-amylphenoxy)butyl] -1,4-

diaza bicyclo [2.2.2]octanium chloride.

( 20) 1,4-di-n-hexadecyl-1,4-diazabicyclo[2.2.2] octanium dithiocyanate.

(21 1,4-di-n-decyl-1,4-diazabicyclo [2.2.2] octanium perchlorate.

(22) 1,IO-decamethylenebis(4-1auryl-1,4-diazabicyclo[2.2.2]octanium)tetrabromide.

(23) n-Octadecyltri-n-butylphosphonium bromide.

(24) n-Hexadecyltriphenylphosphonium bromide.

(25 5 ,5 ,7,7-tetramethyl-2-octenyltri-n-butylphosphonium chloride.

(26) 1-(3,5-dioxo-6-oxa-4-aza)tetracosyltri-n-butylphosphonium bromide.

(27 1,1-dimethyl-1-(n-hexadecyl)hydrazonium perchlorate.

(28) 1,1-dimethyl-1- -stearamidopropyl) hydrazonium chloride. (29)N-cetyl-N-ethylmorpholinium p-ethosulfate.

(30) N-methyl-N-myristyloxymethylmorpholinium p-toluenesulfonate.

(31) 1,4-dimethyl-1,4-di-n-laurylpiperazinium dibromide.

(32) S-n-butyl-S-methyl-S-n-octadecylsulfonium p-toluenesulfonate.

(3 3 S-ethyl-S-methyl-S- ('y-stearoyloxypropyl) sulfoniump-toluenesulfonate.

(34) S,S-di-n-lauryl-S-methylsulfonium thiocyanate.

(35) N,N-dimethyl-N- ,B-dimethylaminoethyl) -N- (n-hexadecyl) ammoniumbromide.

(36) Hexadecyltri-n-butylphosphonium bromide.

(37) N-dodecyl-N-methylrnorpholinium chloride.

(3 8 N-methyl-N-octadecyloxymethylmorpholinium p-t-oluenesulfonate.

(39) Methyltri-n-laurylammonium chloride.

(40) n-Octadecyl-dimethyl-B-hydroxyethyl ammonium bromide.

(41) Sec.-butyl-1,4-diazabicyclo[2.2.2]octanium dibromide.

(42) N-cycloheXyl-N,N-dimethyl-N-(dodecylthiomethyl) ammonium-p-toluenesulfonate.

A wide variety of cationic mordant compounds are useful in the inventionincluding organic quaternary phosphonium salts, organic ternarysulfonium salts and such organic quaternary ammonium salts asmorpholiniurn salts, piperazinium salts, tetraammonium salts,1,4-diazabicyclo[2.2.2]octanium salts and the like. Illustrative of suchcationic mordant compounds are and 4 In the above formulas: R R R R R RR 14 15 R16 17 R18, 19 20 21 23 24 and 25 are alkyl radicals; R is analkyl radical or a hydrogen atom; R R R R R and R are alkyl radicals,substituted alkyl radicals such as alkylamidoalkyl, acyloxyalkyl,alkylphenoxyalkoxyalkyl, alkoxyalkyl, alkylthioalkyl, dialkylaminoalkyl,hydroxyalkyl, and the like, or a cyclohexyl radical; R or R can also beamino radicals; R and R are alkylene radicals; X is an acid anion suchas Br-, Cl, I, CNS-, p-toluenesulfonate, and the like. At least one ofthe substituents on each mordant compound contains a radical having atleast 8 carbon atoms for ballasting purposes. Alkyl and alkyleneradicals in the above formulas generally have from 1 to 22 carbon atoms.

The subject mordant compounds can be utilized either alone or incombinations of more than one mordant. Particularly useful combinationsof mordants are Compounds 1+5, 1-+16, 1+17, 5+23, 5+29, 10-1-17, 29-1-34and others.

The term nonpolymeric used herein with reference to the present mordantcompounds means that the cation of the basic mordant does not haveregularly recurring units containing the cationic group beyond the dimerstructure. However, the ballast group attached to the quaternary orternary atom of the cation group can contain repeating groups, such astetraethoxy, polymethylene, etc.

The mordant compounds useful in the invention can be readily prepared,

The N,N-dialkyl N (fi-hydroxyalkyl)-N-('y-alkylamidoalkyl) ammoniumcompounds can be made by reacting a fatty acid with adialkylaminoalkylamine to form the corresponding amide, which isquaternized with an ethylene halohydrin to form the correspondingquaternized sal-t.

Tetralkylammonium and phosphonium salts can be made by reacting an alkylhalide with a trialkylamine or phosphine.

Alkyl tetraquaternaryammonium salts, e.g., Compound 16, Table I, can bemade by reacting 1 mole of 'tetralkyl alkylenediamine with 1 mole ofalkyl halide pared by the methods described in Erickson U.S. Patents2,694,707 and 2,694,708, issued November 16, 1954, by reacting secondaryamines with his (2-chloroethyl) ether.

The solvent or carrier for the ionic, nonpolymeric mordant compound inthe dispersed phase is a high-boiling, water-immiscible, organic liquidhaving a boiling point above about C. The high-boiling solvent can beused alone in forming the dispersion, or it can be admixed with somelow-boiling organic solvent, i.e., boiling at least about 25 C. belowthe boiling point of the higher-boiling solvent, or a water-solubleorganic solvent, as an auxiliary solvent to facilitate the solution ofthe mordant material. Preferred ranges of proportions of high-boilingsolvent to auxiliary solvent are to M on a weight basis.

Any of the high-boiling, water-immiscible, crystalloidal solventsdescribed on page 2, col. 2 and page 3, col. 1 of U.S. Patent 2,322,027,issued June 15, 1943, can be used. Particularly useful solvents areorganic carboxylic acid esters and organic phosphate esters. Typicalsolvents include di-n-butyl-phthalate, benzyl phthalate, ethyl benzylmalonate, tetrahydrofurfuryl succinate, triphenyl phosphate,tri-o-cresyl phosphate, diphenyl mono-p-tertbutyl phenyl phosphate,monophenyl di-o-chlorophenyl phosphate, tri-p-tert-butylphenylphosphate, 2,4-di-n-amylphenol, and the like.

Typical low-boiling or water-soluble organic auxiliary solvents include,

(1) Substantially water-insoluble low-boiling solvents such as ethyl andbutyl acetates, ethyl propionate, butyl alcohol, ethyl formate,nitroethane, chloroform, etc., and

(2) Water-soluble solvents, such as methyl isobutyl ketone, ,H-ethoxyethyl acetate, fi-but-oxy-B-ethoxy ethyl acetate, tetrahydro-furfuryltadipate, diethylene glycol monoacetate, fi-methoxymethyl acetate,acetonyl acetone, diacetone alcohol, diethylene glycol monomethyl ether,ethylene glycol, dipropylene glycol, acetone, ethanol, acetonitrile,dimethylformamide, dioxane, etc.

The low-boiling or water-soluble solvent can be removed from thedispersion, for example, by air drying a chilled, noodled dispersion, orby continuous water washing.

The hydrophilic polymers useful in our invention as protective colloidsinclude gelatin and its water-soluble derivatives, polyvinyl alcohol,its water-soluble derivatives and copolymers, water-soluble vinylpolymers, such as polyacrylamide, imidized polyacrylamide, etc., andother water-soluble film-forming materials that form water-permeablecoatings, such as colloidal albumin, water-soluble cellulose derivativeslike ethanolamine cellulose acetate, etc. Compatible mixtures of two ormore colloids can be used. Gelatin is preferred.

In preparing dye mordanting compositions of the invention, the mordantis dissolved in a solvent described above and mixed with an aqueoussolution of a hydrophilic colloid. While the amount of solvent utilizedto dissolve the mordant compound can be widely varied, we prefer toutilize proportions of mordant compound to high-boiling solvent in therange of about 1/ .25 to 1/2 on a weight basis. The resultingoil-in-water emulsion is then emulsified or homogenized until themordant dissolved in the solvent is substantially uniformly dispersed infinely-divided droplets, the droplets suitably being less than about 5microns in size, more generally less than about 2 microns in size, andoftentimes in the range of about .5 to less than about 5 microns insize. Small amounts of surfactant compounds can be utilized asdispersants in preparing the solvent dispersions in the hydrophiliccolloid if desired. Suitable surfactants include sodiumdiisopropylnaphthalene sulfonate, sodium laurylsulfonate,p-tert-octylphenoxy diethoxy sulfonate sodium salt, sodiumN-methyl-N-oleyl taurate, diisobutylcresoxyethoxyethyl, dimethyl,benzylammonium chloride, diisobutylphenoxyethoxyethyl, dimethyl,benzylanmmonium chloride and the like.

The mordanting compositions of the invention can be coated on a widevariety of supports including such photographic supports as paper, andfilms of cellulose acetate, polystyrene, polyethylene terephthalate, andthe like.

The mordant layers of our invention are useful in color diffusiontransfer processes such as dye transfer processes in which dyes areimbibed into gelatin relief matrices and subsequently transferred fromthese matrices by diffusion into mordanted receiving layers brought intocontact, such a process being described in Kodak Dye Transfer Process,Kodak Publication No. E-80 of Eastman Kodak Company, Rochester, NewYork.

The mordant layers of our invention are useful for immobilizing andstabilizing the dye images produced in multicolor diffusion transferprocesses, for example, Belgian Patents 578,470, granted November 6-,1959; 585,686, granted June 15, 1960 and 603,747, granted May 31, 1961.In these processes there are produced subtractively colored imagescomposed of dilfusable acid dyes which are formed from nondiffusiblecouplers at the site of silver 6 development. These acid dyes transferby diffusion to a contiguous layer containing a cationic mordant.

The mordant compositions of our invention can also be used forimmobilizing and stabilizing ditfusible dye images in processes, such asdescribed in British Patent 804,971, issued November 26, 1958, andBelgian Patent 607,420, granted August 15, 1961. These processes utilizedye developers which are weak acid dyes also containing in the moleculea developing function. They become immobilized by oxidation at sites ofsilver development, the residual unoxidized dye developer transferringto a receiving layer containing a cationic mordant.

The mordant compositions of our invention may also be used inhydrophilic colloid layers of a photographic element to mordant, forexample, antihalation and filter dyes.

A wide variety of water-soluble acid dyes can be mordanted with themordanting compositions of the invention. Water-soluble acid dyes arewell known materials to those skilled in the art. Such dyes contain acidgroups, for example, carboxylic, sulfonic, ionizable sulfonamido andhydroxy substituted aromatic or heterocyclic groups which lend to thedyes negative charges. Such anionic dyes can be readily immobilized bymeans of the cationic mordant compounds in the mordanting compositionsof the invention.

The following examples further illustrate preferred embodiments of theinvention.

Example I.Preparati0n of mordant-dispersions of the invention Thecationic mordants listed in Table I above were dissolved inWater-immiscible solvents and dispersed in aqueous gelatin solution asdescribed below. A 0.5 gram portion of mordant was dissolved in 0.5 cc.of di-n-butyl phthalate and 3 cc. of ethyl alcohol by heating themixture to the reflux temperature of the mixture. The resulting solutionwas emulsified by mixing it with agitation in a solution of 22 cc. of10% aqueous gelatin solution containing 2 cc. of 5% aqueous solution ofthe surfactant, sodium diisopropylnaphthalene sulfonate. The resultingoil-in-water emulsion was passed through a colloid mill five times tomore finely disperse the suspended droplets of mordanted solution, andwas then chilled to gel the composition, substantially all of thedroplets being lessthan 2 microns in size. The resulting gel was cut upand dried to remove the water and alcohol leaving the mordant highlyconcentrated in the water-immiscible solvent droplets substantiallyuniformly distributed through the composition. The resulting mordantingcompositions can be dried to facilitate storage if desired.

Example II.--Preparati0n of photographic elements containingmordant-dispersions Coatings containing mordant-solvent compositionsusing the mordants listed in Table I above and prepared according toExample I, were made. Two grams of the dry mordanting compositionsdescribed in Example I were redispersed by adding to 21 cc. of water and1.5 cc. of 7.5% sapo-nin solution and heating with stirring at 40 C. Thedispersions were then coated on subbed cellulose acetate film supportsat a wet thickness of 0.009 inch and dried.

Example III.Soluble acid dyes fixed to coatings containingmordant-dispersions of the invention and the improved stability of themordanted dyes The cationic mordant coatings prepared as described inExample II above were used as receiving sheets in the image transfercolor process described in Whitmore et a1. German Patent 1,095,115,published December 16, 1960. The soluble acid dyes from the couplerswere mordanted in these receiving sheets. Each of these couplers, i.e.,I1V below, was incorporated into separate single-layer gelatin silverbromoiodide coatings containing mg./,ft. of coupler, mg./ft. of silver,and 300 mg./ ft. of

gelatin. Samples of these coatings were exposed and developed forminutes at 75 C. in contact with the prepared receiving sheets of theinvention with a color developer solution having the followingcomposition:

Benzyl alcohol, cc. 10.0

Ascorbic acid, g 0.2 Potassium bromide, g. 0.7 Sodium carbonate-1H O, g.20.0 Sodium hydroxide, g. 2.0 4-amino-N-ethyl-N (fi-hydroxyethyl)aniline, g. 10.0

Water to make one liter.

The soluble acid dyes formed during the development by the reaction ofthe couplers with the oxidized developing agent were transferred to andmordanted in the receiving sheets.

COUPLERS I.2-(3,5-disulfobenzamido)-4-(3-octadecylcarbamylphenylthio)-5-methylphenol dispotassium salt. (Cyan dye-forming coupler) II. 1-phenyl-33,5-disulfobenzamido) -4-(2-hydroxy-4- pentadecylphenylazo)5-pyrazolonedipotassium salt. (Magenta dye-forming coupler) III. a-Benzoyl-a- (3-octadecylcarbamylphenylthio -3,5-

dicarboxyacetanilide. (Yellow dye-forming coupler) 1V. l-hydroxy-4- (3-octadecylcarbamylphenylthio -N- ethyl-3',5'-dicarboxy-Z-naphthanilide.(Cyan dye-forming coupler) The resulting mordanted dye images weresubjected to 30 hours xenon arc exposure. Other samples were heated for7 days at 140 F. and 75% relative humidity. The mordanted dye imageswere found to have good density and good stability to heat and light.Table II below compares the stability to light and heat of dye imagesmordanted according to our invention (referred to as Method A below) tosimilar dye images mordanted to the same cationic compounds disperseddirectly in the gelatin coating. These latter were prepared according tothe method of Example I except that the water-immiscible organic solventWas replaced with water (referred to as Method B below).

TABLE II Percent Improve- Percent Improve Wavement in Light ment in Heatlength of Stability of Stability of Mordant Maximum Mordanted DyeMordanted Dye N 0. Coupler Absorption Images at A max. Images at A max.(Table I) Used at the Dye by Using Method by Using Method 0. max.) ACompared to A Compared to in my Method B After Method B After 80 HoursXenon 1 Week at 140 F. Arc Exposure and 75% RH.

As can be observed from the data set out in Table II, mordantingcompositions of the invention prepared with the mordant compounddispersed in a high-boiling solvent can be used to prepare mordanted dyeimages of significantly improved stability to light and heat than canmordanting compositions prepared with the mordant compound dispersed inWater in accordance with usual practree.

Example I V.-C0mparis0n 0f mordant dispersions of the invention todirect gelatin dispersions A receiving sheet Was made according toExample I and 11 (Method A) using Compound #15 of Table I, and a secondreceiving sheet was made using the same compound by incorporating itdirectly into an aqueous gelatin solution according to the methoddescribed in Example III (Method B). Dye images, obtained from CouplersIIV described in Example III and with developing agent 4amino-N-(p-hydroxyethyl)aniline sulfate, in the manner of Example III,were transferred to each of the prepared mordant receiving sheets, andthe resulting mordanted dye images were subjected to the light and heatstability tests described in Example III. Dyes mordanted to Compound 15,incorporated by Method B, underwent substantial loss of dye densitywhereas the dye images mordanted to the same compound incorporated byMethod A (our invention) were substantially more stable to light andheat. Also, Compound 15 was dittusible enough when incorporated byMethod B that it wandered into the printing matrix and reacted with thedye there to form an effective barrier to the passage of further dye,that is to poison the matrix. This undesirable effect did not occur whenCompound 15 was incorporated by the method of our invention.

Example V.Preparati0n of coatings of the invention containing a mixtureof compatible cationic mordants Receiving sheets were made according toExamples I and II, using the following mixtures of cationic mordants ofTable I.

(1) 0.25 g. Compound 17 and 0.25 g. Compound 1 (2) 0.33 g. Compound 10and 0.17 g. Compound 17 (3) 0.17 g. Compound 1 and 0.33 g. Compound 23(4) 0.25 g. Compound 29 and 0.25 g. Compound 34 (5) 0.25 g. Compound 5and 0.25 g. Compound 29 (6) 0.33 g. Compound 5 and 0.1l7 g. Compound 23(7) 0.33 g. Compound 1 and 0.17 g. Compound 5 (8) 0.17 g. Compound 1 and0.33 g. Compound 16 Samples of the mixed mordant receiving sheetsprepared above were used to mordant soluble acid dyes obtained fromCouplers II, III, and IV as described in Example III. Other samples ofthe mixed mordant receiving sheets were used as the receiving sheets tomordant soluble dye developers in the process described in Example I ofWeyerts et al. US. patent application Serial No. 50,932, now abandoned,filed August 22, 1960, corresponding to Belgian patent 607,420, grantedAugust 15, 1961. The resulting dye images gave good color and densityand showed good stability to light and heat.

Example VI.-Filter dye layers containing mordant compositions of ourinvention This example shows the use of our mordant solvent gelatindispersion compositions in filter dye layers. A photographic element wasprepared using a cellulose acetate film support on which was coated ared-sensitized gelatin silver bromiodide emulsion containing the cyandye-forming coupler,2-[u-(2,4-di-tert-amylphenoxy)butyramido]-4,6-dichl0ro-5-methylphenol.Over the red-sensitive emulsion was coated a green-sensitized gelatinsilver bromiodide emulsion containing a magenta dye-forming coupler, l-(p-tert-butylphenoxyphenyl -3- ap-tert-butylphenoxy)propionamido]-5-pyrazolone. Over the greensensitized layer was coated agelatin layer containing tartrazine, a yellow filter dye, mordanted toCompound 17,Table I, incorporated. by the dispersion method as describedin Example II. Over the filter layer was coated a blue-sensitizedgelatin silver bromiodide emulsion layer containing a yellow-dye formingcoupler, a-benzoyl-S-[a- (2,4 di tert amylphenoxy)acetamido]2methoxyacetanilide. All the above silver bromiodide emulsion layers weregold and sulfur sensitized. The multilayer coating 9 was processed to acolor positive by the process described in column 11 of Beavers et al.U.S. Patent 2,944,898, issued July 12, 1960. During color development,the yellow filter dye was removed, leaving the residual mordant in aphotographically inactive condition in the solvent dispersion filterlayer.

Example VII.Use of an integral mordant layer in a multilayer imagetransfer coating This is an example of the use of an integral mordantreceiving layer containing the mordant-solvent composition of ourinvention in a sensitive element containing silver halide emulsionlayers and color couplers to fix in said element the soluble dye imagesformed by color development. A multilayer color element was preparedhaving the following order of layers coated on a paper support:

(1) A gelatin mordant layer containing Compound 17 (Table I)incorporated as described in Example II above.

(2) A stripping layer of cellulose ether phthalate.

(3) A fogged gelatin silver halide emulsion layer containing the magentadye-forming coupler, 1-phenyl-3-(3,5- disulfobenzamido) 4 (4octadecyloxyphenylazo) 5- pyrazolone,

(4) A green-sensitized gelatin silver halide emulsion layer containingthe development inhibitor-releasing compound,1-hydroxy-4-(2-nitrophenylthio) -N- [a- 2,4-di-tertamylphenoxy) butyl]-2-naphthamide.

(5) A fogged gelatin silver halide emulsion layer containing the cyandye-forming coupler,2-(3,5-disulfobenzamido)-5-methyl-4-(4-octadecyloxyphenylazo)phenol,dipotassium salt.

(6) A red-sensitized gelatin silver halide emulsion layer containing thedevelopment inhibitor-releasing compound of layer 4.

(7) A gelatin filter layer containing yellow colloidal silver.

(8) A fogged gelatin silver halide emulsion layer containing the yellowdye-forming coupler, 1-hydroxy-4-{4- [3 methyl 4 (1,5 disulfo 3naphthylazo) 1 pyrazol-S-onyl] phenylazo}-N- [5- 3-pentadecylphenoxy)butyl]-2-naphthamide, dipotassium salt.

(9) A top gelatin silver halide emulsion layer containing thedevelopment inhibitor-releasing compound of layer 4.

The above photographic element was exposed to an image and developed for3 minutes at 70 F. in a developing solution of the followingcomposition:

Sodium carbonate (anhydrous), g Sodium hexametaphosphate, g. 2 Benzylalcohol, cc. 1O 4 amino N ethyl N ([3 hydroxyethyl) aniline sulfate, g.2

Water to make one liter.

The soluble dye images, formed in the silver halide layers, diffusedinto the integral mordant layer which was then stripped from theemulsion layers to yield a print having mordanted dye images of gooddensity and good stability to light and heat.

Example VIII .--Photographic emulsion layers containing mordantcompositions of the invention 1) A red-sensitized gelatin silver halideemulsion layer containing the cyan dye-forming coupler2-[u-(2,4-tertamylphenoxy) acetamido] 4,6 dichloro 5 methylpihe- Theprepared photographic element was exposed to an image and developed for10 minutes at 70 F. in a developing solution having the followingcomposition:

. G. Sodium sulfite (anhydrous) 2 Sodium carbonate (anhydrous) 20Potassium bromide 1 4-amino-N,N-diethyl-3-methylaniline HCl 2 Water tomake one liter.

The soluble dye image formed in the magenta layer diffused to themordant-containing layers to give mordant magenta dye images ofincreased stability to light and heat when compared to non-difiusiblemagenta dyes derived from organic solvent soluble couplers, such as 1 (ptert butylphenoxyphenyl) 3 [a (ptertbuty-lphenoxy)propionamido]-5-pyrazolone and others disclosed, forexample, in Porter U.S. Patent 2,369,489, issued February 13, 1945.Organic solvent soluble cyan and yellow couplers can also be replacedwith respective cyan and yellow image transfer couplers in a multilayerelement of the type described in this example using appropriate mordantlayers to fix the soluble dyes formed during development.

Thus, mordanting compositions having particular utility in preparingcolor photographic products result when cationic mordant compounds aredissolved in high-boiling solvents and the solvents are dispersed insmall droplets in hydrophilie colloids. Such mordanting compositionshave been demonstrated to have utility for mordanting water-soluble aciddyes. Dyes mordanted in accordance with the invention have excellentheat and light stability.

This invention has been described in detail with particular reference topreferred embodiments thereof, but it will be understood that variationsand modifications can be eifected within the spirit and scope of theinvention as described hereinabove and as defined in the appendedclaims.

I claim:

1. In a photographic process for mordanting an acid dye image, theimprovement which comprises mordanting said dye image in a mordantinglayer comprising a hydrophilic organic colloid containing substantiallyuniformly dispersed therein finely divided droplets of a crystalloidal,water-immiscible, organic solvent boiling above about C. containingdissolved therein anonpolymeric organic cationic mordant for acid dyesat a ratio of said mordant to said solvent of about 1/ .25 to 1/ 2 byweight, said mordant being selected from the group consisting ofcompounds having the formulas 1 1 and R25 [attach wherein:

A. 1. 2 5 6 8 R10, 11 14 15 R16, 17 R18, R R R R R and R are alkylradicals, B. R is selected from the group consisting of (1) an aminoradical, (2) an alkyl radical, and (3) a cyclohexyl radical, C. R R R Rand R are selected from the group consisting of (1) an alkyl radical,and (2) a cyclohexyl radical, D. X is an acid anion, and E. R and R arealkylene radicals;

said mordant being ballasted with at least one substituent having atleast 8 carbon atoms.

2. In a photographic process for mordanting an acid dye image, theimprovement which comprises mordanting said dye image in a mordantinglayer comprising a hydro philic organic colloid containing substantiallyuniformly dispersed therein finely divided droplets of a cryst-alloidal,water-immiscible, organic solvent boiling above about 175 C. containingdissolved therein a nonpolymeric organic cationic mordant for acid dyesat a ratio of said mordant to said solvent of about 1/ .25 to 1/2 byWeight, said mordant having the formula wherein R is an alkyl radicaland X is an acid anion, at least one R having at least 8 carbon atoms.

3. A process as described in claim 2 wherein the mordant is methyltri-n-laurylamrnonium p-toluenesulfonate.

4. A process as described in claim 2 wherein the mordant isN,N-dimethyl-N-(fl-hydroxyethyl)-N-('y-stearamidopropyl)ammoniumdihydrogen phosphate.

5. In a photographic process for mordanting an acid dye image, theimprovement which comprises mordanting said dye image in a mordantinglayer comprising a hydrophilic organic colloid containing substantiallyuniformly dispersed therein finely divided droplets of a crystalloidal,water-immiscible, organic solvent boiling above about 175 C. containingdissolved therein a nonpolymeric organic cationic mordant for acid dyesat a ratio of said mordant to said solvent of about 1/ .25 to 1/2 byweight, said mordant having the formula wherein R is an alkyl radicaland X is an acid anion, at least one R having at least 8 carbon atoms.

6. A process as described in claim 5 wherein the mordant isN-cetyl-N-ethylmorpholinium pethosulfate.

7. In a photographic process for mordanting an acid dye image, theimprovement which comprises mordanting said dye image in a mordantinglayer comprising a hydrophilic organic colloid containing substantiallyuniformly dispersed therein finely divided droplets of a crystalloidal,

water-immiscible, organic solvent boiling above about 175 C. containingdissolved therein a nonpoly-meric organic cationic mordant for acid dyesat a ratio of said mordant to said solvent of about 1/ .25 to 1/2 byWeight, said mordant having the formula wherein R is an alkyl radicaland X is an acid anion, at least one R having at least 8 carbon atoms.

8. A process as described in claim 7 wherein the mordant is1,4-dihexadecyl-1,4-diazabicyclo[2.2.2]octanium dichloride.

9. In a photographic process for mordanting an acid dye image, theimprovement which comprises mordanting said dye image in a mordantinglayer comp-rising a hydrophilic organic colloid containing substantiallyuniformly dispersed therein finely divided droplets of a crystalloidal,water-immiscible, organic solvent boiling above about C. containingdissolved therein a nonpolymeric organic cationic mordant for acid dyesat a ratio of said mordant to said solvent of about 1/ .25 to 1/2 byweight, said mordant having the formula wherein R is an alkyl radical, Ris an alkylene radical and X is an acid anion, at least one of R and Rhaving at least 8 carbon atoms.

10. A process as described in claim 9 wherein the mordant is17,17,20,20,31,31,34,34-octamethyl-l7,20,31,34-tetrazapentacontaniumtetrabromide.

11. In a photographic color diffusion transfer process wherein an aciddye is transferred imageiwise by diffusion to a mordanting receptionlayer, the improvement which comprises utilizing as said reception layera layer comprising a hydrophilic organic colloid containingsubstantially uniformly dispersed therein finely divided droplets of acrystalloidal, water-immiscible, organic solvent boiling above about 175C. containing dissolved therein a nonpolymeric organic cationic mordantfor said acid dye at a ratio of said mordant to said solvent of about l/.25 to 1/2 by weight, said mordant being selected from the groupconsisting of compounds having the formula 1 2 5 R5 8 10 11 14 15 R16,17 R18, R R R R R and R are alkyl radicals, B. R is selected from thegroup consisting of (1) an amino radical, (2) an alkyl radical, and (3)a cyclohexyl radical, C. R R R R and R are selected from the groupconsisting of (1) an alkyl radical, and (2) a cyclohexyl radical,

D. X is an acid anion, and

R and R are alkylene radicals; said mordant being ballasted with atleast one substituent having at least 8 carbon atoms.

12. A photographic process as described in claim 11 wherein a solventfor the mordant selected from the group consisting of (1) awater-soluble organic solvent, and

(2) a substantially water-insoluble organic solvent having a boilingpoint at least about 25 C. below the boiling point of the solventboiling above about 175 C. is used as an auxiliary solvent with thesolvent boiling above about 175 C.

and

13. A process as described in claim 11 wherein the solvent boiling aboveabout 175 C. is selected from the group consisting of an organiccarboxylic acid ester and an organic phosphate ester.

14. In a photographic color diffusion transfer process wherein an aciddye is transferred imageiwise by diffusion to a mordanting receptionlayer, the improvement which comprises utilizing as said reception layera layer comprising gelatin containing substantially uniformly dispersedtherein finely divided droplets of a crystalloidal, water-immiscible,organic solvent boiling above about 175 C. containing dissolved thereina nonpolymeric organic cationic mordant for said acid dye at a ratio ofsaid mordant to said solvent of about 1/ .25 to 1/ 2 by weight, saidmordant being selected from the group consisting ofOctadecyltri-nbutylammonium bromide, Tet-radecyltri-nbutylammoniumbromide, 0ctadecyltri-n-octylammonium bromide,Octade'cyltri-n-decylaminonium bromide, Methyltri-n-laurylammoniump-toluenesulfonate, (6) Methyltri-n-decylamrnonium p-toluenesulfonate,(7) Tetra-n-octylanrrnonium bromide,

(8) Tetra-n-decylammonium bromide,

(9) Tetra-n-laurylammonium bromide,

( 10) N,N-dimethyl-N-( B-hydroxyethyl) -N-('y-steara'midopropy-Dammonium dihydrogen phosphate,

( 1 1) 'N,N-dimethyl-'N-(thhydroxyethyl) -('y-stearoyloxypropyl)ammonium chloride,

( 12) N,N-dimethyl-N-( B hydroxyet-hyl)-N-(p-.tertoctylphe-noxydiethoxyethyl) ammonium methosulfonate,

( 13 -N,N-dirnethyl-N-(fl-hydroxyethyl)-N-(p-tertoctylphenoxytetraethoxyethyl)ammonium methosulfonate,

( 14) N, N-dimethyl N- fi-hydroxyethyl) -N-(N-methyly-stearamidopropyl)ammonium bromide,

(15 Cetyltrimethylammonium bromide,

(16) 17,17,20,20,31,31,34,34-octamethyl17,20,31,34-

tetrazapentacontaniumtetrabrornide,

(17) 1,4-dihexadecyl-1,4-diazabi-cyclo [2.2.2] octanium dichloride,

(18) 1,4-didodecyl-1,4-diazabicyclo [2.2.2] octanium ptoluene sulfonate,

(19) 1,4- bis -(2,4-di-tert-amylphenoxy)butyl] -1,4-

diazabicyclo[2.2.2]octanium chloride,

(20) 1,4-di-n-hexadecyl1,4-diazabicyclo[2.2.2]octanium dithiocyanate,

(21 1,4-di-n-decyl-l,4-diazabicyclo [2.2.2]octanium perchlorate,

(22) 1,10-decamethylenenbis(4-lauryl-1,4-diazabicyclo[2.2.2]octanium)tetrabromide,

(2 3) n-Octadecyltri-n butylphosphonium bromide,

(24) n-Hexadecyltriphenylphosphonium bromide,

(25) 5,5,7,7-tetramethyl-2-octenyltri-n butylphosphonium chloride,

(26) 1-'(3,5-dioxo-6-4-aza)tetracosyltri-n butylphosphonium bromide,

(27) l,1-dimethyl-1-(n-hexadecyDhydrazoniurn perchlorate,

(2'8) 1,1-dimethyl-1 ('y-stearamidopropyl) hydraz-oniu-m chloride,

(29) N-cety-l-N-ethylmorpholinium p-ethosulfate,

(30) N-methyl N-myristyloxymethylmorpholinium ptoluenesulfonate,

(31) 1,4-dimethyl-1,4-di-n-lau-rylpiperazinium dibromide,

(32) S-n-butyl-S-=methyl-S-n-octadecylsulfonlium p-toluenesulfonate,

(3 3 S-ethyl-S-methyl-S-('y-stearoyloxypropyl) sulfoniump-toluenesulfonate,

(34) S,S-di-n-lauryl-S-me:thylsulfonium thiocyanate,

(35 N ,N-dimethyl-N- B-di-methylaminoethyl) -N- (nheXadecyDammoniumbromide,

(36) Hexadecyltri-n-butylphosphonium bromide,

(37) -N-dodecyl-N-methylmorpholinium chloride,

(38) N-methyl-N-octadecy'loxy'methylmorpholinium ptoluenesulfonate,

(39) Methyltri-n-laurylammonium chloride,

(40) n-Octadecyl-dimethyl-fi-hydroxyethyl ammonium bromide,

(41) Sec-butyl-l,4-diazabicyclo[2.2.2]octanium dibromide, and

(42 N-cycloheXy-N-N-dimethyl N- dodecylthiomethyl) ammoniump-toluenesulfonate.

15. A photographic element comprising a photographic support havingcoated thereon a rnordantiing layer comprising a hydrophilic organiccolloid containing substantially uniformly dispersed therein finelydivided droplets of a crystalloidal, water-immiscible, organic solventboiling above about C. containing dissolved therein a nonpolymericorganic cationic mordant for acid dyes at a ratio of said mordant tosaid solvent of about l/.25 to 1/2 by weight, said mordant beingselected from the group consisting of compounds having the formulas R2 aRa R l 1'+-R X, R I I+-R I I+ R-4X- K X1 [R14N/ N-R 12X- r ls 21a, aciaX R6 \RIB 1 12a and R25 [R2l s+ R26]X- wherein:

A 1 2 5 6 8 10 11 14 15 R16 17 R18, R R R R R and R are alkyl radicals,B. 'R is selected from the group consisting of (1) an amino radical, (2)an alkyl radical, and (3) a cyclohexyl radical, C. R R R R and R areselected from the group consisting of (1) an alkyl radical, and

(2) a cyclohexyl radical,

D. X is an acid anion, and

E. R and R are alkylene radicals; said mordant being ballasted with atleast one substituent having at least 8 carbon atoms.

16. A photographic element as described in claim 15 wherein a solventfor the mordant selected from the group consisting of (1) awater-soluble organic solvent, and

(2) a substantially water-insoluble organic solvent having a boilingpoint at least about 25 C. below the boiling point of the solvent aboveabout 175 C.

is used as an auxiliary solvent with the solvent boiling above about 175C.

17. A photographic element as described in claim 15 wherein the solventboiling above about 175 C. is selected from the group consisting of anorganic carboxylic acid ester and an organic phosphate ester.

13. A photographic element comprising a photographic support havingcoated thereon a mordant-lug layer comprising a hydrophilic organiccolloid containing substantially uniformly dispersed therein finelydivided droplets of a crystalloidal, water-immiscible, organic solventboiling above about 175 C. containing dissolved therein a nonpolyrnericorganic cationic mordant for acid dyes at a ratio of said mordant tosaid solvent of about 1/.25 to 1/2 by weight, said mordant having thewherein R is an alkyl radical and X is an acid anion, at least one Rhaving at least 8 carbon atoms.

19. A photographic element comprising a photographic support havingcoated thereon a mordanting layer comprising a hydrophilic organiccolloid containing substantially uniformly dispersed therein finely divided droplets of a crystalloidal, water-immiscible, organic solventboiling above about 175 C. containing dissolved therein a nonpolymericorganic cationic mordant for acid dyes at a ratio of said mordant tosaid solvent of about 1/.25 to 1/2 by weight, said mordant having theformula wherein R is an alkyl radical and X is an acid anion, at leastone R having at least 8 carbon atoms.

21. A photographic element comprising a photographic support havingcoated thereon a mordanting layer comprising a hydrophilic organiccolloid containing substantially uniformly dispersed therein finelydivided droplets of a crystalloidal, water-immiscible, organic solventboiling above about 175 C. containing dissolved therein a nonpolymericorganlc cationic mordant for acid dyes at a ratio of said mordant tosaid solvent of about 1/.25 to 1/2 by weight, said mordant having theformula wherein R is an alkyl radical, R is an alkylene radical and X isan acid anion, at least one of R and R having at least 8 carbon atoms.

22. A photographic element comprising a photographic support havingcoated thereon a mordanting layer compnising a hydrophilic organiccolloid containing substantially uniformly dispersed therein finelydivided droplets of a crystalloidal, water-immiscible, organic solventboiling above about C. containing dissolved therein a mixture ofnonpolymeric organic cationic mordants for acid dyes of (1) at least onemordant selected from the group consisting of (a) N,N-dimethylN-(,8hydroxyethyl) N-(ystearamidopropyl)ammonium dihydrogen phosphate,

(b) Methyl tri-n-laurylammonium p-toluenesulfonate,

(c) 1,4-dihexadecyl 1,4 diazabicyclo[2.2.2]octanium dichloride,

(d) 17,17,20,20,31,31,34,34 octamethyl 17,20,31,34-tetrazapentacontanium tetrabromide, and

(e) N-cetyl-N ethylrnorpholinium ethosulfate;

and

(2) at least one mordant selected from the group consisting of (a)octadecyl-tri-mbutylammonium bromide, (b)octade-cyl-tri-n-ibutylphosphoniurn bromide,

and (c) S,S,-di-n-laury1 S methylsulfoni-um thiocyanate; the ratio ofsaid mordants to said solvent being about 1/.25 to 1/2 by Weight.

References Cited by the Examiner UNITED STATES PATENTS 1,981,292 11/1934Todd et a1. 106135 2,482,917 9/1949 Kaplan 106-135 2,852,382 9/1958I-llingsworth et al. 9697 2,868,077 1/1959 Ryan 88--65 3,065,074 11/1962Rogers 9629 3,148,062 9/1964 Whit-more et a1. 9697 3,201,254 8/1965Reynolds et al. 96107 FOREIGN PATENTS 607,420 8/ 1961 Belgium.

NORMAN G. TORCHIN, Primary Examiner. G. H. BJORGE, I. T. BROWN,Assistant Examiners.

11. IN A PHOTOGRAPHIC COLOR DIFFUSION TRANSFER PROCESS WHEREIN AN ACIDDYE IS TRANSFERRED IMAGEWISE BY DIFFUSION TO A MORDANTING RECEPTIONLAYER, THE IMPROVEMENT WHICH COMPRISES UTILIZING AS SAID RECEPTION LAYERA LAYER COMPRISING A HYDROPHILIC ORGANIC COLLOID CONTAININGSUBSTANTIALLY UNIFORMLY DISPERSED THEREIN FINELY DIVIDED DROPLETS OF ACRYSTALLOIDAL, WATER-IMMISCIBLE, ORGANIC SOLVENT BOILING ABOVE ABOUT175*C. CONTAINING DISSOLVED THEREIN A NONPOLYMERIC ORGANIC CATIONICMORDANT FOR SAID ACID DYE AT A RATIO OF SAID MORDANT TO SAID SOLVENT OFABOUT 1/.25 TO 1/2 BY WEIGHT, SAID MORDANT BEING SELECTED FROM THE GROUPCONSISTING OF COMPOUNDS HAVING THE FORMULA